EP0438375A2 - Dérivés d'acides phosphoniques et d'acides thiophosphoniques - Google Patents

Dérivés d'acides phosphoniques et d'acides thiophosphoniques Download PDF

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EP0438375A2
EP0438375A2 EP91810008A EP91810008A EP0438375A2 EP 0438375 A2 EP0438375 A2 EP 0438375A2 EP 91810008 A EP91810008 A EP 91810008A EP 91810008 A EP91810008 A EP 91810008A EP 0438375 A2 EP0438375 A2 EP 0438375A2
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group
atoms
alkyl
substituted
phenyl
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EP0438375A3 (en
EP0438375B1 (fr
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Hermann O. Dr. Wirth
Hans-Helmut Friedrich
Kay Stefan Dr. Gröninger
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
    • C07F9/6539—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6536—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and sulfur atoms with or without oxygen atoms, as the only ring hetero atoms
    • C07F9/6539—Five-membered rings
    • C07F9/6541—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems

Definitions

  • the invention relates to new compounds from the series of phosphonic acids and thionophosphonic acid derivatives, new compositions containing these phosphonic acids and thionophosphonic acid derivatives, new production processes, and the use of sulfur-containing phosphonic acids and thionophosphonic acid derivatives in organic materials, the chemical, oxidative or actinic degradation are subject.
  • Za. Obshch. Khim. 37 (2), 489-92 (1967) is, for example, the compound of the formula EtSCH 2 CH (OH) PO (OEt) 2 , prepared from a molar mixture of EtSCH 2 CHO and (EtO) 2 PHO by treatment with EtONa / EtOH , known.
  • the compound is said to have an insecticidal effect on flies.
  • T has the meaning of -S-, particularly preferably -S or
  • R I and R 2 are identical or different and are an alkyl group having 1 to 18 C atoms, an alkenyl group having 2 to 18 C atoms Phenyl, a phenyl group substituted with one or two C 1 -C 9 alkyl groups, a phenylalkyl group with 7 to 9 C atoms, a cycloalkyl group with 5 to 12 ring C atoms or a cycloalkyl group with 5 to 12 ring C atoms Are atoms which are substituted by an alkyl group having 1 to 4 carbon atoms, or wherein R 1 and R 2 together form a straight-chain alkylene group having 2 to 5 carbon atoms, a straight-chain alkylene group having 2 to 5 carbon atoms, which are represented by one or two alkyl groups having 1 to 4 carbon atoms or by a group -CH 2 -O-C 1 -C 9
  • R 4 means straight-chain alkylene with 1 to 10 C-atoms or straight-chain alkylene with 1 to 10 C-atoms, that with one or two alkyl groups with 1 to 4 C-atoms is substituted, or straight-chain alkylene with 2 to 10 C atoms, which is interrupted by 1 to 5-S-or-O- or alkylene with 2 to 10 C atoms, which has one or two alkyl groups with 1 to 4 C- Atoms is substituted and interrupted by 1 to 5 -S- or -O-, or R 4 has the meaning of a bivalent heterocycle with 5 to 6 ring members with 1 to 3 nitrogen
  • Preferred compounds of the formula are those in which R 1 and R 2 are identical or different and represent a straight-chain or branched-chain alkyl group having 2 to 12 carbon atoms, phenyl or cyclohexyl, or R 1 and R 2 together are a straight-chain C 2 or C 3 alkylene group or with a C 1 -C 4 alkyl group substituted dimethylene or trimethylene group, a di-C 1 -C 4 alkyl substituted dimethylene or trimethylene group or a -CH 2 -StC 4 H 9 substituted dimethylene or trimethylene group or a group of formula represent.
  • R 1 and R 2 are identical or different and are C 2 -C 8 -alkyl and in particular ethyl, i-propyl, n-butyl, t-butyl, 2-ethylhexyl or n-octyl, or R 1 and R 2 together represent dimethylene, 1-methyldimethylene, 1-ethyldimethylene, 2,2-dimethyltrimethylene or 2-ethyl-2-n-butyltrimethylene.
  • the particularly preferred compounds of the formula also include those in which R I and R 2 are identical are.
  • R 3 is methyl, phenyl or -CH 2 -SR 4 "are expedient, where R 4" is an alkyl group having 2 to 12 carbon atoms or is where Z has the meaning given and R 3 'is -H, alkyl having 1 to 4 carbon atoms or phenyl and R 1 ' and R 2 'are the same and an alkyl group having 1 to 8 carbon atoms, phenyl or cyclohexyl represent or R 1 and R 2 'together represent a straight-chain C 2 or C 3 alkylene group or a C 1 -C 4 alkyl-substituted dimethylene or trimethylene group, a di-C 1 -C 4 alkyl-substituted dimethylene or trimethylene group or one with -CH 2 -StC 4 Hg or -CH 2 -O-iC 8 H 17 substituted dimethylene or trimethylene group.
  • R 4 is suitable are an alkyl group having 1 to 12 C atoms, a phenyl group, a benzyl group or an alkyl group having 2 to 8 C atoms which is substituted by an OH group or an alkyl group having 2 to 12 C atoms which are interrupted by an -O- or -S-, or an alkyl group having 2 to 18 C atoms which are interrupted by an -O- or -S- and substituted by an -OH group or a group of the formula -R 6 -COOR 7 , where R 6 represents a straight-chain alkylene group having 1 to 3 C atoms and R 7 represents an alkyl group having 4 to 8 C atoms, or represents a cyclohexyl group, or R 4 represents a group of the formula in which X is oxygen or sulfur and R 1 " 'and R 2 " are the same and alkyl with 1 to 8 C atoms or R
  • R 4 has the meaning of a heterocycle with 5 to 6 ring members with 1 to 3 nitrogen atoms or a heterocycle with 5 to 6 ring members with one or two nitrogen atoms and a further hetero atom
  • R 3 has the meaning of C 1 -C 4 alkyl or phenyl and R 4 has the meaning of R 4 ' , where R 4 ' C i - C 4 alkyl, a heterocycle with 5 ring members and one or two nitrogen atoms, a heterocycle with 5 ring members and one nitrogen atom and with one or two additional heteroatoms from the series S or O, one of the above heterocycles with fused Benzo ring or C 3 -C 12 alkyl, substituted with an -OH and interrupted with 1 or 2 O or S.
  • R o , R 1 , R 2 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 in compounds of the formula I are alkyl having 1 to 18 carbon atoms, examples are methyl, ethyl, propyl , Isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl , Hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, 1,1,3,3-tetramethyl
  • Alkyl radicals having 1 to 12 carbon atoms are expedient, which can be seen from the examples given above. Alkyl groups with 1 to 12 carbon atoms are preferred, for which again examples can be taken from the above list. Ethyl, i-propyl, n-butyl, t-butyl, 2-ethylhexyl, n-octyl and dodecyl are particularly preferred for R 1 and R 2 .
  • Examples of phenyl or naphthyl groups substituted by at least one C 1 -C 9 as radicals R °, R 1 or R 2 or of R 8 , R 9 , R 10 , R 11 , R i2 and R 13 as mono-, di- or tri-C 1 -C 9 alkyl-substituted phenyl are methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, isopropylphenyl, t-butylphenyl, di-t-butylphenyl, 2,6-di-t-butyl-4-methylphenyl or nonylphenyl.
  • Examples of a phenylalkyl group with 7 to 9 carbon atoms for R °, R 1 , R 2 , R 10 , R 11 , R 12 and R 13 are benzyl and 2-phenylethyl, with benzyl being preferred.
  • Examples of R 10 , R 11 and R 12 as C 7 -C 9 phenylalkyl mono-, di- or tri-C 1 -C 4 -alkyl substituted on the phenyl are methylbenzyl, dimethylbenzyl and t-butylbenzyl.
  • R o , R 1 , R 2 , R 10 , R 11 , R 12 and R 13 represent a cycloalkyl group with 5 to 12 ring C atoms
  • examples are cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl , with cyclohexyl being preferred.
  • R o , R 1 , R 2 and R 13 are a cycloalkyl group having 5 to 12 ring C atoms which is substituted by at least one, advantageously 1 to 3, preferably 1 or 2, alkyl groups having 1 to 4 C atoms, or if R 10 , R 11 or R 12 are mono-, di- or tri-C 1 -C 4 -alkyl-substituted C 5 -C 12 cycloalkyl groups, examples are methylcyclopentyl, dimethylcyclopentyl, 2- or 4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl or t-butylcyclohexyl. Cyclohexyl substituted with an alkyl group, for example methylcyclohexyl, is preferred.
  • R ° can also represent -H.
  • R 1 and R2 together form a straight-chain alkylene group with 2 to 5 carbon atoms, corresponding examples are ethylene, trimethylene, tetramethylene or pentamethylene. Ethylene and trimethylene are preferred.
  • R 1 and R 2 together form a straight-chain alkylene group with 2 to 5 C atoms which is substituted by at least one alkyl group with 1 to 8 C atoms
  • examples of these are 1-methyl-1,2-ethanediyl, 1-ethyl 1,2-ethanediyl, 2,2-dimethyl-1,3-propanediyl or 2-ethyl-2-n-butyl-1,3-propanediyl.
  • R 1 and R 2 together form, for example, a straight-chain alkylene group having 2 to 5 carbon atoms, which is substituted by a group -CH 2 -SC 1 -C 9 alkyl. This is preferably a group of the formula
  • R 1 and R 2 together form a group of the formula where R 5 is an alkyl group having 1 to 4 carbon atoms and e is a number of 0, 1 or 2, preferred examples are o-phenylene, 4-methyl-o-phenylene or 4-t-butyl-o-phenylene .
  • Q means -0- or-NR ° -, with -0- being preferred.
  • Preferred for R ° is -H or C 1 -C 4 alkyl, preferably t-butyl.
  • R 1 and R 2 together preferably form a dimethylene radical.
  • R 1 ', R 1 " , R 1"' , R 2 ', R 2 "and R 2"' can be taken from the lists given.
  • the meanings of R 1 are expediently the same as for R 1 ' , R 1 " or R 1 "' or for R 2 the same as for R 2 ', R2" or R2 "' .
  • R 4 ' , R 1 , R 2 , R ° or R 13 represent an alkenyl group with 2 to 18 C atoms, examples are vinyl, allyl, 2-methallyl, 2-butenyl, trans-2-butenyl, 2 -Hexenyl, trans-2,4-hexadienyl, resp.
  • Examples of C 3 -C 6 alkenyl for R 10 are allyl and 2-methylallyl.
  • R 11 and R 12 as -OH-substituted C 2 -C 4 -alkyl are 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl and 4-hydroxybutyl, 2-hydroxyethyl is preferred.
  • R 11 and R 12 as C 1 -C 8 alkoxy-substituted C 2 -C 4 alkyl are 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl .
  • the methoxy group is preferred as the alkoxy group.
  • R 11 and R 12 as C 2 -C 4 alkyl substituted by di- (C i -C 4 alkyl) amino, preferably by dimethylamino or diethylamino, are 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethylaminobutyl.
  • R 11 and R 12 form a 5- to 7-membered heterocycle together with the nitrogen atom linking them, which may optionally also contain further heteroatoms from the series of N and O, examples are pyrrolidyl, piperidyl, piperazinyl, morpholinyl, N- Methylpiperazinyl, hexahydroazepinyl and perhydroazepinyl.
  • the substituent R 3 in formula 1 means, inter alia, alkyl having 1 to 4 carbon atoms. Examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-butyl or tert-butyl. Methyl is preferred.
  • R 4 in formula I has the meaning of R 4 ', which can mean alkyl having 1 to 18 C atoms. Examples of such alkyl groups can be found in the corresponding list for R 1 and R 2 . N-Butyl, t-butyl, i-butyl, n-octyl, sec.-octyl, t-nonyl, sec.-dodecyl or t-dodecyl are preferred.
  • R 4 ' when this is an alkyl group with 1 to 18 C atoms, which is substituted by at least one, advantageously 1 to 5, OH group, or an alkyl group with 2 to 18 C atoms by at least one, expediently 1 to 5, -S- or -O- is interrupted, or an alkyl group having 3 to 18 C atoms which is substituted by at least one, advantageously 1 to 5, OH groups and by at least one, expediently 1 to 5 -S- or-0-interrupted, are 2-hydroxyethyl, 2-hydroxy-n-propyl, -CH 2 -CH 2 -CH 2 -S-tC 4 H 9 , -CH 2 -CH 2 -CH 2 -O-iC 8 H 17 ,
  • R 4 represents a group of the formula -R 6 COOR 7
  • R 6 is an alkylene group with 1 to 6 C atoms
  • R 7 is an alkyl group with 1 to 12 C atoms.
  • R 6 are methylene, ethylene, trimethylene, tetramethylene or hexamethylene, for R 7 methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, etc.
  • Preferred for a group of the formula -R 6 COOR 7 are, for example, -CH 2 -COO-tC 4 H 9 or -CH 2 COO-iC 8 H 17 .
  • R 4 represents a cycloalkyl group with 5 to 12 ring C atoms or a cycloalkyl group with 5 to 12 ring C atoms which is substituted with at least one alkyl group with 1 to 4 C atoms, corresponding examples can be found and preferences above, as exemplified for R 1 and R 2 .
  • R 41 can mean sulfur or oxygen, oxygen is preferred.
  • R 1 and R 2 in such substituents can have the meanings and preferences mentioned at the outset.
  • Preferred are substituents of the above type, in which R 1 and R 2 are the same.
  • Preferred R 1 and R 2 in such substituents are C 1 -C 8 alkyl and in particular ethyl, n-butyl, i-butyl, n-octyl and 2-ethylhexyl.
  • Further preferred for R 1 and R 2 together are alkylene radicals and substituted alkylene radicals, ethylene and trimethylene and 2,2-dimethyl-1,3-propanediyl being mentioned.
  • R 4 ' is a group of the formula where X is oxygen or sulfur
  • Z and R 3 ', and R 1 and R 2 have the meanings mentioned.
  • Preferred for R 3 '-H, methyl and phenyl, for R 1 and R 2 which are preferably identical, are alkyl groups with 1 to 8 C atoms or for R 1 and R 2 together a straight-chain alkylene group with 2 or 3 C- Atoms or with one or two C 1 -C 4 alkyl groups substituted straight-chain alkylene groups with 2 or 3 C atoms.
  • Z is preferably -H.
  • R 4 can be straight-chain alkylene having 1 to 10 carbon atoms. Examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene or decamethylene, with ethylene being preferred.
  • Examples of straight-chain alkylene groups with 1 to 10 C atoms which are substituted by at least one, suitably by 1 to 3 and preferably by 1 or 2, alkyl groups having 1 to 4 C atoms, as also mentioned for R 4 , are 1- Methyl 1,2-ethanediyl, 1- Ethyl-1,2-ethanediyl, 2,2-dimethyl-1,3-propanediyl or 2-methyl-2-n-butyi-1,3-propanediy).
  • Examples of straight-chain alkylene groups with 2 to 10 C atoms which are interrupted by at least one —S— or —O—, as mentioned for R 4 can be the formulas —CH 2 —CH 2 —CH 2 7CH 2 7, -CH 2 -CH 2 -O-CH 2 -CH 2 -, -CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 - or -CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 - have.
  • R 4 has the meaning of alkenylene with 2 to 10 carbon atoms, examples are vinylene, methyl vinylene, octenyl ethylene or 2-butene-1,4-diyi.
  • R 4 has the meaning of a divalent heterocycle with 5 to 6 ring members with 1 to 4 nitrogen atoms or a bivalent heterocycle with 5 to 6 ring members with one or two nitrogen atoms and a further hetero atom from the series O or S, or
  • compositions result e.g. by the choice of components b), compounds of general formula 1, as described above, in their expedient and preferred embodiments.
  • Suitable organic material can be found, for example, in the list below.
  • the incorporation of the compounds of formula 1 according to the invention and, if necessary, further additives into the organic material takes place according to methods known per se. It can be carried out, for example, by mixing in the products according to the invention and, if appropriate, further additives using the methods customary in industry, before or during shaping, or else by applying the dissolved or dispersed compounds to the polymer, if appropriate with subsequent evaporation of the solvent.
  • the products according to the invention can also be added to the materials to be stabilized in the form of a masterbatch, which contains them for example in a concentration of 2.5 to 25% by weight.
  • the products according to the invention can also be added before or during the polymerization or before crosslinking.
  • the compounds of formula I can e.g. in amounts of 0.01 to 10% by weight, expediently 0.1 to 5% by weight and preferably 0.1 to 3% by weight, based on the organic material, are used in the organic material.
  • the materials stabilized in this way can be used in various forms, e.g. as foils, fibers, tapes, molding compounds, profiles or as binders for paints, adhesives or putties.
  • the compounds of the formula I are valuable additives in organic materials.
  • the above organic materials and especially the synthetic polymers can contain other additives.
  • additional additives are:
  • Alkylated monophenols e.g. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl- 4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol, 2, 6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol.
  • 2,6-di-tert-butyl-4-methylphenol 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-
  • Alkylated hydroquinones e.g. 2,6-di-tert-butyl-4-methoxyphenoi, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.
  • Hydroxylated thiodiphenyl ethers e.g. 2,2'-thio-bis- (6-tertbutyl-4-methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- (6-tertbutyl-3- methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol).
  • Alkylidene bisphenols e.g. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis- [ 4-methyl-6- (a-methylcyclohexyl) phenol], 2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis- (6-nonyl-4- methylphenol), 2,2'-methylene-bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert-butylphenol), 2,2'- Ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis- [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis-bis- [
  • benzyl compounds e.g. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, bis- (3,5-di-tert-butyl-4-hydroxybenzyl) - sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetic acid, bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, 1,3,5-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di - tert.butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, Ca salt of 3,5-di-tert-
  • esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.
  • esters of ⁇ - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols such as with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol , Tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.
  • Esters of ⁇ - (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols e.g. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide.
  • Amides of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid e.g. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) tri methylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
  • Esters of optionally substituted benzoic acids e.g. 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert.butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert.butyl-4.-hydroxybenzoic acid-2,4-di -tert.butylphenyl ester, 3,5-di-tert.butyl-4-hydroxybenzoic acid hexadecyl ester.
  • benzoic acids e.g. 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert.butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-d
  • Acrylates such as ⁇ -cyano-ß, ß-diphenylacrylic acid, ethyl or isooctyl ester, a-carbomethoxy cinnamic acid methyl ester, a-cyano-ß-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, a-carbomethoxy-p-methoxy cinnamic acid methyl ester, N- (ß-Carbomethoxy-ß-cyanovinyl) -2-methyl-indoline.
  • Nickel compounds e.g. Nickel complexes of 2,2'-thio-bis- [4 (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n- Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as those of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 2-hydroxy-4-methyl -phenyl-undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
  • additional ligands such as n- Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibut
  • Sterically hindered amines e.g. Bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate n-butyl-3,5-di-tert-butyl-4 -hydroxybenzyl-malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product from N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris- (2, 2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperid
  • Oxalic acid diamides e.g. 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'di-tert.
  • butyloxanilide 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2 '-ethyl-5,4'-di-tert.butyl-oxanilide, mixtures of o- and p-methoxy and of o- and p-ethoxy-di-substituted oxanilides.
  • Metal deactivators such as N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl ) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide.
  • Phosphites and phosphonites e.g. Triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris- (nonylphenyl) -phosphite, trilaurylphosphite, trioctadecylphosphite, distearyl-pentaerythritol-diphosphite, tris- (2,4-di-tert-butylphenyl) -phosphite, diisodhritol-di (ditithritol-bisphit) .butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert.butylphenyl) -4,4'-biphenylene-diphosphonite, 3,9-bis- (2,
  • Peroxide destroying compounds e.g. Esters of ⁇ -thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakec (ßcap-dodecapro-dodecapro-dodecapro-dodecapro).
  • Esters of ⁇ -thio-dipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakec
  • Polyamide stabilizers e.g. Copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids ren, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, antimony catecholate or tin catecholate.
  • Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids ren, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, antimony cate
  • Nucleating agents e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
  • Fillers and reinforcing agents such as e.g. Calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
  • additives such as Plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
  • Preferred organic material is mentioned in point 28 above.
  • this includes the functional fluids, which include, for example, the lubricants, the hydraulic fluids and the metalworking fluids.
  • lubricants e.g. the lubricating oils for internal combustion engines, the hydraulic oils, the compressor oils and the so-called industrial lubricants, which include, for example, the groups of turbine oils, both for steam and gas turbines.
  • the lubricating oils for internal combustion engines include, in particular, the lubricating oils which operate the lubrication circuit of an internal combustion engine from the crankcase or dry sump.
  • Internal combustion engines mean, for example, reciprocating or rotary piston engines with internal or external ignition (diesel or petrol principle).
  • the lubricants, hydraulic fluids and metalworking fluids in question are based, for example, on mineral or synthetic oils, as well as oils derived from living nature or mixtures thereof.
  • the lubricants are familiar to the person skilled in the art and are found in the relevant specialist literature, for example in Dieter Klamann, "Lubricants and Related Products” (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, "The Lubricant Pocket Book” (Dr. Alfred Wilsonhig- Verlag, Heidelberg, 1974) and in “Ullmann's Encyclopedia of Technical Chemistry", Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).
  • the lubricants are especially oils. Fats, for example based on a mineral oil, are included.
  • the mineral oils are based in particular on hydrocarbon compounds.
  • Examples of synthetic lubricants include lubricants based on the aliphatic or aromatic carboxyl esters, the polymeric esters, the polyalkylene oxides, the phosphoric acid esters, the polya-olefins or the silicones, a diester of a dibasic acid with a monohydric alcohol, e.g. Dioctyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monohydric acid or with a mixture of such acids, e.g.
  • mineral oils e.g. Poly-a-olefins
  • hydraulic oils but also lubricating oils and greases can be based on animals and plants and, for example, animal tallow, sperm, fish and bone oil, palm kernel oil, rapeseed oil, linseed oil, rapeseed oil, soybean oil, coconut oil, nut oil and their modified, such as epoxidized and sulfurized, forms can be specified.
  • the lubricants can additionally contain other additives which are added in order to further improve the basic properties of lubricants; these include: antioxidants, metal passivars, rust inhibitors, viscosity index improvers, pour point depressants, dispersants, detergents, high-pressure additives and anti-wear additives.
  • Aliphatic or aromatic phosphites esters of thiodipropionic acid or thiodiacetic acid, or salts of dithiocarbamide or dithiophosphoric acid.
  • metal passivators e.g. for copper
  • metal passivators e.g. for copper
  • Triazoles benzotriazoles and their derivatives, tolutriazoles and their derivatives, 2-mercaptobenzthiazole, 2-mercaptobenztriazole, 2,5-dimercaptobenztriazole, 2,5-dimercaptobenzthiadiazole, 5,5'-methylenebisbenzotriazole, 4,5,6,7-tetrahydrobenztriazole, salicylides -propylenediamine, salicylaminoguanidine and its salts.
  • rust inhibitors are:
  • Organic acids, their esters, metal salts and anhydrides e.g. : N-oleoyl sarcosine, sorbitan mono-oleate, lead naphthenate, alkenyl succinic anhydride, e.g. Dodecenylsuccinic anhydride, alkenylsuccinic acid partial esters and partial amides, 4-nonylphenoxyacetic acid.
  • Nitrogen-containing compounds e.g. : I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, e.g. oil-soluble alkylammonium carboxylates.
  • Heterocyclic compounds e.g. :
  • phosphorus-containing compounds e.g. : Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc dialkyldithiophosphates.
  • sulfur containing compounds e.g. : Barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates.
  • viscosity index improvers examples are:
  • Polyacrylates polymethacrylates, vinyl pyrrolidone / methacrylate copolymers, polyvinyl pyrrolidones, polybutenes, olefin copolymers, styrene / acrylate copolymers, polyethers.
  • pour point depressants examples are:
  • dispersants / surfactants / detergents examples are
  • Compounds containing sulfur and / or phosphorus and / or halogen such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl di- and tri-sulfides, triphenyl phosphorothionates, diethanolaminomethyltolyltriazole, di (2-ethylhexyl) aminol.
  • the organic materials contain 0.01 to 10% by weight, expediently 0.05 to 5% by weight, preferably 0.05 to 3% by weight and in particular 0.1 to 2% by weight, in total from at least one compound of the formula as mentioned above
  • compositions according to the invention have in the case of thermoplastics and elastomers outstanding processing and use properties and the compounds of formula 1 according to the invention can therefore be referred to as processing and use additives for thermoplastics and elastomers.
  • the compounds of the formula I according to the invention have the properties of a multifunctional additive and improve the high-pressure and friction wear properties in an outstanding manner. Particularly noteworthy is the effect on reducing frictional wear and corrosion (rust) protection.
  • the present invention also encompasses the use of the compounds of the formula as mentioned above in organic materials. Appropriate and preferred uses can be derived from expedient and preferred compounds of the formula I and organic materials designated as expedient and preferred.
  • Compounds of the formula in which Z has the meaning of -COR 13 , -COOR 13 or-CONHR 13 can be prepared in a manner known per se, for example from compounds of the formula in which Z has the meaning of -H, by acylation with acylation agents, by conversion with corresponding anhydrides, acid chlorides, carbonic acid chlorides or by addition to corresponding isocyanates.
  • the method can also be carried out with the aid of phase transfer technology.
  • M can represent, for example, as alkali metal Li, Na, K, Rb or Cs, preferably Na or K and in particular Na.
  • Alkaline hydroxides such as sodium or potassium hydroxide
  • alkali alcoholates such as sodium or potassium methylate, ethylate or propylate
  • Sodium hydroxide, potassium hydroxide, sodium methylate or sodium ethylate is expediently used as the catalyst.
  • the amount of the catalyst is not critical; Based on the compound of the formula II, it is expedient to use 0.001 to 20% by weight, preferably 0.01 to 10% by weight, of the catalyst for the first reaction stage.
  • the second reaction stage is advantageously carried out using stoichiometric amounts of an alkali captide M-SR 4 or MSM or M- (S) qM, where M and R 4 have the meanings given and q denotes 2, 3, 4 or 5.
  • the second reaction stage, the thiolytic exchange of halogen in compounds of the formula III, can also be carried out, for example, with the corresponding SH compounds, it being possible to use stoichiometric amounts of tertiary amines.
  • Suitable tertiary amines have the formula where R a , R b and R °, independently of one another, are linear or branched, Ci-Cs-alkyl radicals, C 3 -C 8 alkenyl radicals, cycloalkyl having 5 to 12 ring C atoms, phenyl or Ci-C4alkyl-substituted phenyl, furthermore, for example, pyridine derivatives and other heterocyclic bases can be used.
  • tertiary amines examples include triethylamine, tributylamine or triisopropylamine, and pyridine or 1,8-diazobicyclo [5.4.0] undec-5-ene (DBU).
  • tertiary amines are the so-called Hünig bases, accordingly compounds which e.g. Can bind hydrogen chloride, but are incapable of ⁇ -elimination.
  • a solvent can be used in both reaction stages, the amount per se not being critical and solvents such as toluene, xylene, tetrahydrofuran, dioxane, diglyme, t-butyl methyl ether, etc. can be used.
  • the reactions are expediently carried out without a solvent, and the reactants can also act as solvents with one another.
  • the quantitative ratios of compounds of the formula II to compounds of the formula III in the first reaction stage are not critical per se, the compounds are expedient, based on the equivalents, in a stoichiometric ratio of 1 to 0.8 to 1.2, preferably in one Ratio of 1 to 0.95 to 1.05 applied
  • the stoichiometric ratio of one equivalent of the formula IV to one equivalent of the formula V 1 can be from 0.8 to 1.2, preferably from 1 to 0.95 to 1.05.
  • reaction temperatures and reaction times are not critical in both stages and the process is generally carried out between 0 ° C. and the reflux temperature of the respective reaction mixture.
  • the temperature is expediently kept between 0 ° C., preferably 20 ° C. and 40 ° C., preferably 35 ° C., and the temperature is allowed to rise between 20 ° C. and the reflux temperature towards the end of the reaction.
  • the reaction times are generally between 20 minutes and 2 hours, the reactants mostly being largely converted after 20 to 40 minutes and being stirred for a further 20 minutes to one hour, for example.
  • the reaction usually proceeds in two stages.
  • the reaction can also be carried out in a one-pot process.
  • the second step can also be carried out with the corresponding alkali captaptides, which are easily accessible via the alkali alcoholates in an inert solvent.
  • Preferred compounds are obtainable, for example, by the processes described below in a second implementation stage:
  • Another method of preparing compounds of the general formula according to the present invention is the reaction of epoxides of the formula X. wherein Q, X, R °, R l , R 3 have the meanings given (R ° 'with the same definition as R °, R ° and R °' the same or different) with compounds of the formula XI HTR 4 (XI) (XI ) wherein T and R 4 have the meanings given for compounds of the general formula Ib
  • n is a number from 2 or 3
  • a corresponding compound of the formula Ia can be prepared, for example, using the following equation:
  • the compounds of the formula VI can be obtained, for example, by reacting a compound of the formula R 4 -SM where R 4 and M have the meanings given above, with a compound of the formula III wherein R 3 and Hal have the meanings given above, for example in the presence of a catalyst, expediently a basic catalyst and in particular a phase transfer catalyst.
  • reaction mixture is stirred for 30 minutes and the solvent is distilled off under vacuum.
  • the residue is suspended in 200 ml of diethyl ether, extracted with 60 ml of water and sodium bicarbonate solution, the organic phase is dried and concentrated again to the residue.
  • the melting point is then 109-111 ° C.
  • 2-Dodecylthio-1-hydroxy-1-methylethanephosphonic acid di-ethyl ester is also prepared by the method described above, but the phosphorous acid di-octyl ester is replaced by 10.6 g (76.8 mmol) of phosphorous acid di-ethyl ester replaced. 23.4 g (77% of theory) of crude product are obtained.
  • Corrosivity to copper is also determined using the ASTM standard method D 130.
  • a polished copper strip is immersed in an oil pattern and left in it at 120 ° C for three hours. After this test period, the copper strip is removed from the oil, cleaned and compared with the standard values.
  • the table shows the results of 1% solutions of the particular compound according to the invention in a base oil (Catenex® P 941 from Shell), containing 0.03% of a commercially available copper passivator of the type 1- (di-2-ethylhexyl) - aminomethyltolutriazole.
  • the copper strips are assessed in 4 stages, using the "ASTM Copper Strip Corrosion Standards":
  • B represents a fine division within the number groups 1 to 4 and means the shadow formation on the samples.
  • the rating A comes before B, B before C, etc.
  • Example 28 The product according to Example 16 is tested according to the ASTM standard method D 665 B with regard to the rust-preventing properties in turbine oils in the presence of water.
  • the test method is designed such that 300 ml of the oil to be tested, containing the additives according to the invention, and 30 ml of synthetic sea water are stirred in a vessel at 60 ° C. for 24 hours. A cylindrical steel sample is immersed in the oil to be tested.
  • the test procedure is designed to determine the ability of a steam turbine oil to prevent rusting of iron parts should water get into the oil.
  • the degree of corrosion of the steel cylinder samples is measured.
  • O no rust
  • 3 means a rusted sample.
  • intermediate digits indicate the intermediate stages with regard to the degree of rusting.
  • the concentration of the compound according to Example 16 is 0.25% in a base oil.
  • the sample shows no rust after the test and is rated 0.
  • a sample that is tested in the base oil, without compounds according to the invention, is rusted and is rated 3.

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EP91810008A 1990-01-18 1991-01-09 Dérivés d'acides phosphoniques et d'acides thiophosphoniques Expired - Lifetime EP0438375B1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
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WO1995014385A1 (fr) * 1993-11-24 1995-06-01 Agrevo Uk Limited Pesticides a base de phosphonate de triazole
US6489476B1 (en) 1998-09-09 2002-12-03 Metabasis Therapeutics, Inc. Heteroaromatic compounds containing a phosphonate group that are inhibitors of fructose-1,6-bisphosphatase
JP2009235346A (ja) * 2008-03-28 2009-10-15 Bridgestone Corp 加硫促進剤、ゴム組成物およびそれを用いたタイヤ

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US5617941A (en) * 1993-12-22 1997-04-08 Aisin Seiki Kabushiki Kaisha Force-receiving plate for friction device
IL149887A0 (en) * 1999-12-22 2002-11-10 Metabasis Therapeutics Inc Novel bisamidate phosphonate prodrugs
US7563774B2 (en) * 2000-06-29 2009-07-21 Metabasis Therapeutics, Inc. Combination of FBPase inhibitors and antidiabetic agents useful for the treatment of diabetes
CN1329491C (zh) * 2003-12-30 2007-08-01 中国科学院兰州化学物理研究所 含膦酸酯官能团的离子液体及其制备方法和用途
BRPI0514372A (pt) * 2004-08-18 2008-06-10 Metabasis Therapeutics Inc inibidores de tiazol de frutose 1, 6-bisfosfatase
US8466096B2 (en) * 2007-04-26 2013-06-18 Afton Chemical Corporation 1,3,2-dioxaphosphorinane, 2-sulfide derivatives for use as anti-wear additives in lubricant compositions
FR2974096A1 (fr) * 2011-04-14 2012-10-19 Michelin Soc Tech Composition de caoutchouc comprenant un derive de thiazole
JP7012660B2 (ja) 2016-04-01 2022-02-14 ノームズ テクノロジーズ インコーポレイテッド リン含有修飾イオン性液体
CN110915037B (zh) 2017-07-17 2023-11-07 诺姆斯科技公司 含磷电解质

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EP0100718A1 (fr) * 1982-07-29 1984-02-15 Sanofi S.A. Produits anti-inflammatoires dérivés de l'acide méthylène-diphosphonique et leur procédé de préparation
EP0328488A2 (fr) * 1988-02-12 1989-08-16 Ciba-Geigy Ag Disulphides asymétriques dans des compositions lubrifiantes

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014385A1 (fr) * 1993-11-24 1995-06-01 Agrevo Uk Limited Pesticides a base de phosphonate de triazole
US6489476B1 (en) 1998-09-09 2002-12-03 Metabasis Therapeutics, Inc. Heteroaromatic compounds containing a phosphonate group that are inhibitors of fructose-1,6-bisphosphatase
US7312219B2 (en) 1998-09-09 2007-12-25 Metabasis Therapeutics, Inc. Heteroaromatic inhibitors of fructose 1,6-bisphosphatase
JP2009235346A (ja) * 2008-03-28 2009-10-15 Bridgestone Corp 加硫促進剤、ゴム組成物およびそれを用いたタイヤ

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DE59107135D1 (de) 1996-02-08
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CA2034283A1 (fr) 1991-07-19
US5550276A (en) 1996-08-27
JPH0517490A (ja) 1993-01-26

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